CN115449133A - Composite gel and preparation method and application thereof - Google Patents
Composite gel and preparation method and application thereof Download PDFInfo
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- CN115449133A CN115449133A CN202210997001.2A CN202210997001A CN115449133A CN 115449133 A CN115449133 A CN 115449133A CN 202210997001 A CN202210997001 A CN 202210997001A CN 115449133 A CN115449133 A CN 115449133A
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- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001879 gelation Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 78
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 69
- 239000011707 mineral Substances 0.000 claims abstract description 69
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004033 plastic Substances 0.000 claims abstract description 20
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 239000000499 gel Substances 0.000 claims description 113
- 239000002002 slurry Substances 0.000 claims description 31
- 238000007731 hot pressing Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 18
- 229920001661 Chitosan Polymers 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000005022 packaging material Substances 0.000 claims description 12
- 239000010455 vermiculite Substances 0.000 claims description 12
- 229910052902 vermiculite Inorganic materials 0.000 claims description 12
- 235000019354 vermiculite Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 6
- 229910021647 smectite Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
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- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 239000002734 clay mineral Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 3
- 239000000017 hydrogel Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 9
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- 238000012545 processing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a composite gel and a preparation method and application thereof. The composite gel comprises a hydrophilic polymer and a two-dimensional mineral material dispersed in the hydrophilic polymer, wherein the clay mineral material is dispersed in the hydrophilic polymer in the form of the two-dimensional material, and can be compounded with the hydrophilic polymer of an organic material under highly ordered arrangement by utilizing the advantages of extremely high geometric anisotropy and high modulus of the two-dimensional material, so that the effect of enhancing the mechanical property is realized, and the composite gel has high strength. The composite gel has low cost and environmental protection, can be used for developing degradable high-performance plastic substitutes, and can be recycled, and when the composite gel is recycled, the attenuation rate of the mechanical strength of the product is lower than 5%, and the attenuation rate of the water stability is lower than 5%. The invention also provides a preparation method and application of the composite gel.
Description
Technical Field
The invention belongs to the technical field of degradable materials, and particularly relates to a composite gel and a preparation method and application thereof.
Background
"white pollution" caused by the use of disposable plastic products in large quantities is a major challenge in the environmental field, and nearly one fourth of plastic wastes are discarded or incinerated and enter the natural environment as solid wastes or are enriched in organisms in the form of micro-plastics, thus causing serious ecological problems. It is expected that 20% of the world's oil will be used to make plastic products by the middle of this century, further exacerbating the energy crisis, and the carbon emissions generated during processing and manufacturing will account for 15% of the total emissions worldwide. For sustainable development, developing raw materials and preparing plastic substitutes which are green and environment-friendly in the processing process and can be completely degraded after being used are one of solutions with great prospects.
The hydrogel has the advantages of wide source, strong adjustability and environmental friendliness, and is considered as a possible plastic substitute. However, the water content of the traditional hydrogel is more than 70%, the solid content is low, the mechanical properties such as strength and modulus are poor, and the traditional hydrogel cannot replace disposable products such as plastic bags and lunch boxes which are in large demand. Modification of hydrogels by inorganic materials is a common mechanical enhancement means. In the related art, the mechanical strength of the inorganic material modified hydrogel still cannot meet the actual requirement due to the weak acting force of the inorganic material and the organic phase.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides the composite gel which is low in cost, environment-friendly and high in mechanical strength.
The invention also provides a method for preparing the composite gel.
The invention also provides application of the composite gel in preparation of plastic substitutes.
The invention also provides application of the composite gel in preparation of a packaging material.
The invention provides a composite gel, which comprises a hydrophilic polymer and a two-dimensional mineral material dispersed in the hydrophilic polymer, wherein the hydrophilic polymer comprises at least one of chitosan, sodium alginate and gelatin, and the two-dimensional mineral material comprises at least one of kaolinite-serpentine two-dimensional mineral material, smectite two-dimensional mineral material, vermiculite two-dimensional mineral material and mica two-dimensional mineral material.
The invention relates to one of the technical schemes of the composite gel, which at least has the following beneficial effects:
the composite gel comprises a hydrophilic polymer and a two-dimensional mineral material dispersed in the hydrophilic polymer, wherein the two-dimensional mineral material comprises at least one of kaolinite-serpentine two-dimensional mineral material, smectite two-dimensional mineral material, vermiculite two-dimensional mineral material and mica two-dimensional mineral material, the two-dimensional mineral materials are clay mineral materials, and the clay mineral materials are used as one of common substances with abundant reserves on the earth, have the characteristics of easy mining, low price and the like, are completely non-toxic and harmless, and are one of the most ideal raw materials for preparing hydrogel composite materials. If the granular clay mineral is directly added into the gel as an additive of the granules, the mechanical strength of the prepared hydrogel can not meet the actual requirement due to the small specific area of the clay mineral and the weak interaction force with the organic phase. In the invention, the clay mineral material is dispersed in the hydrophilic polymer in the form of a two-dimensional mineral material, and the two-dimensional material has the advantages of great geometric anisotropy and high modulus, can be compounded with the hydrophilic polymer of an organic material under highly ordered arrangement to realize the effect of enhancing the mechanical property, and the composite gel has high strength.
The composite gel provided by the invention is low in cost and environment-friendly, and can be used for developing degradable high-performance plastic substitutes.
The composite gel of the invention can be recycled, and when the composite gel is recycled, the attenuation rate of the mechanical strength of the product is lower than 5%, and the attenuation rate of the water stability (contact angle) is lower than 5%.
The composite gel can be rapidly degraded in soil, and the degradation time is less than 100h.
According to some embodiments of the present invention, the raw materials for preparing the composite gel comprise, in parts by weight:
two-dimensional mineral material: 60 to 85 portions of the mixture of the components,
hydrophilic polymer (b): 10 to 30 portions of the raw materials are mixed,
water: 5 to 10 portions.
According to some embodiments of the invention, the two-dimensional mineral material is vermiculite.
According to some embodiments of the invention the two-dimensional mineral material has a transverse dimension ≧ 2 μm.
The two-dimensional mineral material has a transverse dimension of more than or equal to 2 μm, which is favorable for increasing the action sites of the organic and inorganic phases.
According to some embodiments of the invention, the two-dimensional mineral material is present in an amount of 60 to 85% by weight of the hydrophilic polymer.
The mass percentage of the two-dimensional mineral material in the hydrophilic polymer is 60-85%, and higher breaking strength can be obtained by proper proportion.
According to some embodiments of the invention, the composite gel has a breaking strength of greater than 800MPa.
A second aspect of the invention provides a method of preparing the composite gel, comprising the steps of:
s1: mixing a hydrophilic polymer with a mineral raw material and then grinding to obtain slurry;
s2: after removing oxygen in the slurry, pouring the slurry into a mold, and evaporating water to obtain a crude gel product;
s3: and carrying out hot-pressing treatment on the gel crude product to obtain the composite gel.
The invention relates to a technical scheme in a preparation method of composite gel, which at least has the following beneficial effects:
in the preparation method of the composite gel, the hydrophilic polymer and the mineral raw material are mixed and ground to obtain slurry. In the grinding process, hydrogen bonds and ionic interaction between the monomers and the two-dimensional material are adjusted by virtue of mechanical acting force generated by grinding and the existence of the hydrophilic polymer, the mineral raw material is stripped into two-dimensional sheets from three-dimensional grains, and the two-dimensional mineral material is dispersed in the hydrophilic polymer in the obtained slurry. Then, after removing oxygen in the slurry, pouring the slurry into a mold, and evaporating water to obtain a crude gel product, wherein the two-dimensional mineral material in the crude gel product is mainly dispersed in the gel in a single piece form. After the gel crude product is subjected to hot pressing treatment, the two-dimensional mineral material dispersed in a single sheet form is converted into a multi-sheet superposed form, so that the finally obtained composite gel has good mechanical strength.
According to some embodiments of the invention, in step S1, the mass ratio of the hydrophilic polymer to the mineral raw material is 1.
According to some embodiments of the invention, the milling time is between 12h and 48h.
According to some embodiments of the invention, the milling time is between 24h and 48h.
According to some embodiments of the invention, nitrogen is introduced during the evaporation of water in step S2.
According to some embodiments of the invention, in step S2, the size of the mold may be 10cm × 10cm × 1cm.
According to some embodiments of the invention, the temperature of the hot pressing is between 80 ℃ and 120 ℃.
According to some embodiments of the invention, the temperature of the autoclaving is between 100 ℃ and 120 ℃.
According to some embodiments of the invention, the time of the hot pressing treatment is 20min to 40min.
According to some embodiments of the invention, the time of the hot pressing treatment is 30min to 40min.
The third aspect of the invention provides the application of the composite gel in preparing a plastic substitute.
The invention relates to a technical scheme of application of composite gel in preparing plastic substitutes, which at least has the following beneficial effects:
the composite gel has good mechanical strength and is suitable for preparing various plastic substitutes.
The composite gel can be rapidly degraded in soil, the degradation time is less than 100h, and the composite gel is environment-friendly when being prepared into various plastic substitutes, particularly disposable products.
The fourth aspect of the invention provides the application of the composite gel in preparing packaging materials.
The composite gel has good mechanical strength and is suitable for preparing various packaging materials.
The composite gel can be rapidly degraded in soil, the degradation time is less than 100h, and the composite gel is environment-friendly when being prepared into various packaging materials, particularly disposable packaging materials.
According to some embodiments of the invention, the packaging material comprises "plastic sheet", disposable cutlery box, etc.
Drawings
FIG. 1 is an atomic force microscope test chart.
FIG. 2 is a schematic of the large scale preparation of the sample of example 2.
FIG. 3 is a wide angle X-ray diffraction line of the composite gel of example 2.
FIG. 4 is a graph representing the mechanical strength of composite gels prepared in examples 1, 2 and 3 at various concentrations.
FIG. 5 shows the results of the water and solvent resistance tests of the composite gel prepared in example 2.
FIG. 6 is a thermogravimetric analysis of the composite gel prepared in example 2.
FIG. 7 is a graph showing the analysis of the characteristics of the composite gels prepared in examples 1, 2 and 3, which can be recycled.
Fig. 8 is a graph showing degradation tests of the complex gels prepared in examples 1, 2 and 3.
FIG. 9 is a schematic diagram of the preparation process of the composite gel of the present invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the present invention, the present invention provides a composite gel comprising a hydrophilic polymer and a two-dimensional mineral material dispersed in the hydrophilic polymer, the hydrophilic polymer comprising at least one of chitosan, sodium alginate, and gelatin, the two-dimensional mineral material comprising at least one of a kaolinite-serpentine family two-dimensional mineral material, a smectite family two-dimensional mineral material, a vermiculite family two-dimensional mineral material, and a mica family two-dimensional mineral material.
It can be understood that the composite gel of the present invention comprises a hydrophilic polymer and a two-dimensional mineral material dispersed in the hydrophilic polymer, wherein the two-dimensional mineral material comprises at least one of kaolinite-serpentine two-dimensional mineral material, smectite two-dimensional mineral material, vermiculite two-dimensional mineral material and mica two-dimensional mineral material, the two-dimensional mineral materials are derived from clay mineral material, and the clay mineral material is one of the common materials with abundant reserves on the earth, has the characteristics of easy exploitation, low price and the like, is completely non-toxic and harmless, and is one of the most ideal raw materials for preparing hydrogel composite materials. If the granular clay mineral is directly added into the gel as an aggregate additive, the mechanical strength of the prepared hydrogel cannot meet the actual requirement because the specific area of the clay mineral is small and the acting force with the organic phase is weak. In the invention, the clay mineral material is dispersed in the hydrophilic polymer in the form of a two-dimensional mineral material, and the two-dimensional material has the advantages of great geometric anisotropy and high modulus, can be compounded with the hydrophilic polymer of an organic material under highly ordered arrangement to realize the effect of enhancing the mechanical property, and the composite gel has high strength.
Furthermore, the composite gel provided by the invention is low in cost and environment-friendly, and can be used for developing degradable high-performance plastic substitutes.
In some embodiments of the present invention, the raw materials for preparing the composite gel comprise, by weight:
two-dimensional mineral material: 60 to 85 portions of the mixture of the components,
hydrophilic polymer: 10 to 30 portions of the mixture of the components,
water: 5 to 10 portions.
In some embodiments of the invention, the two-dimensional mineral material is vermiculite.
In some embodiments of the invention the two-dimensional mineral material has a transverse dimension ≧ 2 μm.
It will be appreciated that the two-dimensional mineral material has a transverse dimension of > 2 μm, which facilitates the introduction of a large amount of natural polymer, increasing the site of action of the organic and inorganic phases.
In some embodiments of the invention, the two-dimensional mineral material is present in the hydrophilic polymer in an amount of 60 to 85% by weight.
The mass percentage of the two-dimensional mineral material in the hydrophilic polymer is 60-85%, and higher breaking strength can be obtained by proper proportion.
In some embodiments of the invention, the composite gel has a breaking strength greater than 800MPa.
In still other embodiments of the present invention, the present invention provides a method of making a composite gel comprising the steps of:
s1: mixing a hydrophilic polymer with a mineral raw material and then grinding to obtain slurry;
s2: after removing oxygen in the slurry, pouring the slurry into a mold, and evaporating water to obtain a crude gel product;
s3: and carrying out hot-pressing treatment on the gel crude product to obtain the composite gel.
It can be understood that in the preparation method of the composite gel, the hydrophilic polymer and the mineral raw material are mixed and ground to obtain slurry. In the grinding process, hydrogen bonds and ionic interaction between the monomers and the two-dimensional material are adjusted by virtue of mechanical acting force generated by grinding and the existence of the hydrophilic polymer, the mineral raw material is stripped into two-dimensional sheets from three-dimensional grains, and the two-dimensional mineral material is dispersed in the hydrophilic polymer in the obtained slurry. And then, after removing oxygen in the slurry, pouring the slurry into a mold, evaporating water to obtain a crude gel product, removing impurities with oxidability such as oxygen in the slurry, and dispersing a two-dimensional mineral material in the crude gel product in a form of single pieces after evaporating water to dryness. After the gel crude product is subjected to hot pressing treatment, the two-dimensional mineral material dispersed in a single sheet form is converted into a multi-sheet superposed form, so that the finally obtained composite gel has good mechanical strength.
In some embodiments of the invention, in step S1, the mass ratio of the hydrophilic polymer to the mineral raw material is 1.
In some embodiments of the invention, the milling time is 12 hours to 48 hours.
In some embodiments of the invention, the milling time is between 24h and 48h.
In some embodiments of the present invention, in step S2, nitrogen is introduced during the process of evaporating water.
In some embodiments of the present invention, in step S2, the size of the mold may be 10cm × 10cm × 1cm.
In some embodiments of the invention, the temperature of the autoclave is between 80 ℃ and 120 ℃.
In some embodiments of the invention, the temperature of the autoclave is from 100 ℃ to 120 ℃.
In some embodiments of the invention, the time for the hot pressing is 20min to 40min.
In some embodiments of the invention, the time for the hot pressing is 30min to 40min.
In further embodiments of the present invention, the present invention provides the use of a composite gel in the preparation of a plastic substitute.
The composite gel has good mechanical strength and is suitable for preparing various plastic substitutes.
Specifically, the composite gel disclosed by the invention can be rapidly degraded in soil, the degradation time is less than 100h, and the composite gel is environment-friendly when being prepared into various plastic substitutes, particularly disposable products.
In further embodiments of the present invention, the present invention provides the use of a composite gel in the preparation of a packaging material.
The composite gel has good mechanical strength and is suitable for preparing various packaging materials.
Specifically, the composite gel disclosed by the invention can be rapidly degraded in soil, the degradation time is less than 100h, and the composite gel is environment-friendly when being prepared into various packaging materials, particularly disposable packaging materials.
In some embodiments of the invention, the packaging material comprises plastic sheet material, disposable cutlery boxes, etc.
The technical solution of the present invention will be better understood by referring to the following specific examples.
In the examples, the milling apparatus used is RM 200, leichi Germany.
Example 1
In this example, a composite gel was prepared, and the specific preparation process was:
12.5mL(40g·L -1 ) Adding chitosan solution and 2g vermiculite into a grinder, grinding for 24h to obtain slurry, degassing with nitrogen for 30min to remove oxygen, pouring into a mould of 10cm × 10cm × 1cm, evaporating water, shaping to obtain composite gel, and hot-pressing at 100 deg.C for 30min to obtain the final product labeled C1V4.
Wherein, 40 g.L -1 The chitosan solution of (2%) is a 1L aqueous solution of 2% acetic acid containing 40g of chitosan.
The water is evaporated until the quality is unchanged at room temperature and normal temperature.
Example 2
In this example, a composite gel was prepared, and the specific preparation process was:
25mL(40g·L -1 ) Adding chitosan solution and 2g vermiculite into a grinder, grinding for 24h to obtain slurry, degassing with nitrogen for 30min to remove oxygen, pouring into a mould of 10cm × 10cm × 1cm, evaporating water, shaping to obtain composite gel, and hot-pressing at 100 deg.C for 30min to obtain the final product labeled C1V2.
Wherein, 40 g.L -1 The chitosan solution of (2%) is a 1L aqueous solution of 2% acetic acid containing 40g of chitosan.
The water is evaporated until the quality is unchanged at room temperature and normal temperature.
Example 3
In this example, a composite gel was prepared, and the specific preparation process was:
50mL(40g·L -1 ) Adding chitosan solution and 2g vermiculite into a grinder, grinding for 24h to obtain slurry, degassing with nitrogen for 30min to remove oxygen, pouring into a mould of 10cm × 10cm × 1cm, evaporating water, shaping to obtain composite gel, and hot-pressing at 100 deg.C for 30min to obtain the final product labeled C1V1.
Wherein, 40 g.L -1 The chitosan solution of (2%) is a 1L aqueous solution of 2% acetic acid containing 40g of chitosan.
The water is evaporated until the quality is unchanged at room temperature and normal temperature.
Comparative example 1
The composite gel is prepared by the specific preparation process:
25mL(40g·L -1 ) Adding chitosan solution and 2g of pre-crushed vermiculite (hundreds of micrometers), grinding for 4h to obtain slurry, degassing for 30min with nitrogen to remove oxygen, pouring into a mould of 10cm × 10cm × 1cm, evaporating water, shaping to obtain composite gel, and hot pressing at 100 deg.C for 30min to obtain the final product.
Wherein, 40 g.L -1 The chitosan solution of (2) is 1L of acetic acid aqueous solution containing 40g of chitosan.
The water is evaporated until the quality is unchanged at room temperature and normal temperature.
Performance testing
The composite gels prepared in the examples and the comparative examples are subjected to performance characterization, and specific characterization modes and results are as follows:
and (3) morphological analysis:
the exfoliation effect of the two-dimensional clay was observed with an atomic force microscope (Tapping mode, cyper ES, oxford Instruments, USA) to analyze the thickness and size of the platelets.
The morphology of the lyophilized gel was observed by scanning electron microscopy (Hitachi FE-SEM S-4800 instrument).
And (3) testing the degree of order:
the prepared composite gel was cut into standard specimens for wide angle X-ray scattering (WAXS) measurement (Xenocs Xeuss SAXS/WAXS System).
The prepared composite gel was cut into a standard sample bar (length. Times. Width. Times. Thickness: 14 mm. Times. L0 mm. Times.1 mm), the sample was placed in the center of a plate of a universal material tensile testing machine so as to be kept naturally vertical, and then clamped with a jig at a constant rate (20 mm. Min.) -1 ) And slowly applying the load until the sample bar is broken, measuring the maximum tensile stress strength and the breaking elongation, and calculating corresponding stress and strain data according to the maximum tensile stress strength and the breaking elongation.
And (3) testing the stability of the solvent:
the hydrogel was cut into standard strips (length. Times. Width. Times. Thickness specification: 2 cm. Times.2 cm. Times.1 mm), and then placed in various organic solvents to observe the change in strength of the hydrogel.
And (3) testing thermal stability:
the hydrogel samples were subjected to thermogravimetric analysis (TG/DTA 6300) and observed for changes in composition with increasing temperature.
And (3) testing in a circulating way:
and (3) crushing the sample, adding water, grinding again to obtain slurry, and casting and film-paving again.
And (3) degradable testing:
the hydrogel was cut into standard strips (circular samples of 6cm diameter) and embedded in soil and the degradation effect was observed at 24h intervals.
And (3) analyzing an experimental result:
FIG. 1 is an atomic force microscope photograph showing the effect of mechanical exfoliation of clay minerals with the aid of chitosan. In FIG. 1, a is the atomic structure of the two-dimensional clay (vermiculite), b is the atomic force microscope photograph of the two-dimensional clay after exfoliation, with an average size of the platelets of 2.46 μm and an average thickness of 3.54nm (c and d in FIG. 1).
FIG. 2 is a schematic of the large scale preparation of the sample of example 2. In FIG. 2, a is 6 bottles of 1L slurry, and it can be seen that the slurry is uniformly dispersed and no precipitation occurs; b is a prepared sample picture of 24 multiplied by 0.6cm, which is formed by hot pressing six single sheets; and c is a scanning electron microscope picture, and the oriented arrangement of the lamellar structure in the composite gel can be obviously observed.
FIG. 3 is the wide angle X-ray diffraction lines of the composite gel of example 2, where the composite gel is observed to have an ordered structure with an order of 0.917.
FIG. 4 characterization of mechanical strength of composite gels prepared in examples 1, 2 and 3 at different concentrations. It can be found that the breaking strength of C1V1, C1V2 and C1V4 is 441MPa, 845MPa and 135mpa, respectively, with the highest strength of C1V2 (a in fig. 4) as the concentration of the two-dimensional clay material is changed. In the comparative sample, the strength of the comparative sample was only 226MPa after the mechanical mixing at the same ratio, indicating that the hydrogel prepared had excellent strength (b in FIG. 4).
Fig. 5 is a comparison of the composite gel prepared in example 2, which is soaked in water and organic solvents (alcohols, esters and ethers) for 40 days, and the gel strength is reduced by only 2%, which shows that the prepared gel has good water and solvent resistance.
FIG. 6 is a thermogravimetric analysis of the composite gel prepared in example 2, which shows that the gel is thermally stable before 278 ℃ and the moisture content in the system is determined to be 5%. Decomposition of the polymer occurred before 500 ℃ and finally 67% of the original clay material remained, indicating that the gel produced had good heat resistance.
Fig. 7 is a characteristic analysis of the composite gels prepared in examples 1, 2 and 3 for recycling. Referring to fig. 7, the composite gel of the present invention can be obtained by simply mechanically crushing the finished composite gel, pouring the crushed composite gel into a grinder, adding water to grind and peel off again, to obtain slurry again, and casting again to obtain hydrogel for later use (the casting refers to evaporating water and hot pressing). Tests show that the mechanical strength decay rate of the circulating product is lower than 5%, and the water stability (contact angle) decay rate is lower than 5%. This indicates that the gels prepared have excellent recyclability.
Fig. 8 is a degradation test of the complex gels prepared in examples 1, 2 and 3. Samples of 6cm diameter were buried in the soil and observed at 24h intervals, and after 72h the samples were found to have completely decomposed, indicating that the plastic substitute had good degradation characteristics.
In the preparation method of the composite gel, the hydrophilic polymer and the mineral raw material are mixed and ground to obtain slurry. In the grinding process, hydrogen bonds and ionic interaction between the monomers and the two-dimensional material are adjusted by virtue of mechanical acting force generated by grinding and the existence of the hydrophilic polymer, the mineral raw material is stripped into two-dimensional sheets from three-dimensional grains, and the two-dimensional mineral material is dispersed in the hydrophilic polymer in the obtained slurry. And then, after removing oxygen in the slurry, pouring the slurry into a mold, evaporating water to obtain a crude gel product, removing impurities such as oxygen in the slurry, and after evaporating water to dryness, dispersing a two-dimensional mineral material in the crude gel product into gel mainly in a form of single pieces. After the gel crude product is subjected to hot pressing treatment, the two-dimensional mineral material dispersed in a single sheet form is converted into a multi-sheet superposed form, so that the finally obtained composite gel has good mechanical strength. The above-described preparation process can be referred to fig. 9.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. A composite gel comprising a hydrophilic polymer and a two-dimensional mineral material dispersed within the hydrophilic polymer, the hydrophilic polymer comprising at least one of chitosan, sodium alginate and gelatin, the two-dimensional mineral material comprising at least one of a kaolinite-serpentine family two-dimensional mineral material, a smectite family two-dimensional mineral material, a vermiculite family two-dimensional mineral material and a micaceous family two-dimensional mineral material.
2. Composite gel according to claim 1, characterized in that the two-dimensional mineral material has a transverse dimension of > 2 μm.
3. The composite gel of claim 1, wherein the two-dimensional mineral material is present in the hydrophilic polymer in an amount of 60-85% by weight.
4. The composite gel of any one of claims 1 to 3, wherein said composite gel has a breaking strength of greater than 800MPa.
5. A method of preparing a composite gel according to any one of claims 1 to 4, comprising the steps of:
s1: mixing a hydrophilic polymer with a mineral raw material and then grinding to obtain slurry;
s2: after removing oxygen in the slurry, pouring the slurry into a mold, and evaporating water to obtain a crude gel product;
s3: and carrying out hot-pressing treatment on the gel crude product to obtain the composite gel.
6. The method according to claim 5, wherein the grinding time is 12 to 48 hours.
7. The method according to claim 5, wherein the temperature of the hot pressing treatment is 80 ℃ to 120 ℃.
8. The method according to claim 5, wherein the time for the hot pressing is 20min to 40min.
9. Use of a composite gel according to any one of claims 1 to 4 in the preparation of a plastic substitute.
10. Use of a composite gel according to any one of claims 1 to 4 in the manufacture of packaging materials.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594402A (en) * | 2004-07-09 | 2005-03-16 | 武汉理工大学 | Method for preparing polymer/laminated silicate nano composite materials |
| EP1525078A2 (en) * | 2002-07-26 | 2005-04-27 | Multibase S.A. | Method for obtaining nanocomposite thermoplastic materials by exfoliating laminar mineral particles in a polymer matrix and nanocomposite materials obtained thereby |
| JP2010095586A (en) * | 2008-10-15 | 2010-04-30 | Kawamura Inst Of Chem Res | Method for forming organic-inorganic composite hydrogel |
| CN108620033A (en) * | 2018-05-22 | 2018-10-09 | 华南理工大学 | Iron modification chitosan/vermiculite Composite that is a kind of while removing zwitterion heavy metal and its preparation and application |
| CN111186823A (en) * | 2020-02-19 | 2020-05-22 | 清华-伯克利深圳学院筹备办公室 | Polymer-assisted preparation method of two-dimensional material and composite material thereof |
| CN112266497A (en) * | 2020-11-04 | 2021-01-26 | 北京航空航天大学 | Shell-like light high-strength composite material and preparation method thereof |
| CN113817195A (en) * | 2021-11-02 | 2021-12-21 | 浙江优可丽新材料有限公司 | Chitin @ MXene @ Ni chain thin film material and preparation method and application thereof |
| CN114074927A (en) * | 2020-08-18 | 2022-02-22 | 清华大学深圳国际研究生院 | Two-dimensional material, preparation method thereof and composite membrane |
-
2022
- 2022-08-19 CN CN202210997001.2A patent/CN115449133A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1525078A2 (en) * | 2002-07-26 | 2005-04-27 | Multibase S.A. | Method for obtaining nanocomposite thermoplastic materials by exfoliating laminar mineral particles in a polymer matrix and nanocomposite materials obtained thereby |
| CN1594402A (en) * | 2004-07-09 | 2005-03-16 | 武汉理工大学 | Method for preparing polymer/laminated silicate nano composite materials |
| JP2010095586A (en) * | 2008-10-15 | 2010-04-30 | Kawamura Inst Of Chem Res | Method for forming organic-inorganic composite hydrogel |
| CN108620033A (en) * | 2018-05-22 | 2018-10-09 | 华南理工大学 | Iron modification chitosan/vermiculite Composite that is a kind of while removing zwitterion heavy metal and its preparation and application |
| CN111186823A (en) * | 2020-02-19 | 2020-05-22 | 清华-伯克利深圳学院筹备办公室 | Polymer-assisted preparation method of two-dimensional material and composite material thereof |
| CN114074927A (en) * | 2020-08-18 | 2022-02-22 | 清华大学深圳国际研究生院 | Two-dimensional material, preparation method thereof and composite membrane |
| CN112266497A (en) * | 2020-11-04 | 2021-01-26 | 北京航空航天大学 | Shell-like light high-strength composite material and preparation method thereof |
| CN113817195A (en) * | 2021-11-02 | 2021-12-21 | 浙江优可丽新材料有限公司 | Chitin @ MXene @ Ni chain thin film material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEI WANG等: "Pb(ΙΙ) removal from water using porous hydrogel of chitosan-2D montmorillonite", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》, vol. 128, pages 85 * |
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